EP2989243B1 - A rfl-free dipping composition providing high performance for cord fabrics - Google Patents
A rfl-free dipping composition providing high performance for cord fabrics Download PDFInfo
- Publication number
- EP2989243B1 EP2989243B1 EP14736054.9A EP14736054A EP2989243B1 EP 2989243 B1 EP2989243 B1 EP 2989243B1 EP 14736054 A EP14736054 A EP 14736054A EP 2989243 B1 EP2989243 B1 EP 2989243B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butadiene
- styrene
- high performance
- material composition
- providing high
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 238000007598 dipping method Methods 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 39
- 239000004744 fabric Substances 0.000 title claims description 32
- 229920000126 latex Polymers 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 36
- 239000004816 latex Substances 0.000 claims description 34
- 239000004593 Epoxy Substances 0.000 claims description 22
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000005060 rubber Substances 0.000 claims description 22
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 17
- 239000005056 polyisocyanate Substances 0.000 claims description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000002174 Styrene-butadiene Substances 0.000 claims description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 239000011115 styrene butadiene Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- -1 aromatic isocyanates Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000002952 polymeric resin Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 6
- 241000531908 Aramides Species 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229920003235 aromatic polyamide Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229930003836 cresol Natural products 0.000 claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000036541 health Effects 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000000524 functional group Chemical class 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 claims description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 claims description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 claims description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 claims description 2
- CYMRPDYINXWJFU-UHFFFAOYSA-N 2-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=CC=C1C(O)=O CYMRPDYINXWJFU-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 claims description 2
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 claims description 2
- JTHGIRIGZAGNOX-UHFFFAOYSA-N 4-pentan-2-ylphenol Chemical compound CCCC(C)C1=CC=C(O)C=C1 JTHGIRIGZAGNOX-UHFFFAOYSA-N 0.000 claims description 2
- ZUTYZAFDFLLILI-UHFFFAOYSA-N 4-sec-Butylphenol Chemical compound CCC(C)C1=CC=C(O)C=C1 ZUTYZAFDFLLILI-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 claims description 2
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009931 harmful effect Effects 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 230000007774 longterm Effects 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002964 rayon Substances 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
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- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000000835 fiber Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 5
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- ISCIUIIRLMFIQC-UHFFFAOYSA-N C=CC=C.C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 Chemical compound C=CC=C.C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 ISCIUIIRLMFIQC-UHFFFAOYSA-N 0.000 description 1
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- 208000003251 Pruritus Diseases 0.000 description 1
- 206010043521 Throat irritation Diseases 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
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- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical group ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
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- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/404—Yarns or threads coated with polymeric solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
- D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/04—Compacting
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Definitions
- the present invention relates to an environmentally friendly dipping material composition, which forms an interphase between the synthetic fiber that is used in the production of cord fabric and rubber and thus bonds the said two structures to each other.
- Cord fabric is used as tire reinforcement material. Since the chemical structures of synthetic fibers used in cord fabric production and rubber are considerably different from each other, the said materials are incompatible with each other in terms of their chemical and physical structures. Synthetic fibers have high strength and low elongation whereas rubbers are polymeric materials which have high elongation and low strength. The polar groups (amide, hydroxyl and carbonyl groups) present in the structure of the synthetic fibers are incompatible with the non-polar structures of the rubber. This incompatibility present in the state of the art is eliminated with water-based Resorcinol-Formaldehyde-Latex (RFL) adhesive solutions which form a phase between the cord and the rubber and enable the rubber and the fiber to be attached to each other.
- RTL Resorcinol-Formaldehyde-Latex
- RFL Main function of RFL is to serve as an adhesive bonding two incompatible structures by forming a phase between fiber and rubber.
- RF functional group in RFL is attached to the polar groups of fiber while Latex (L) group is attached to the fiber by vulcanization, and thus the rubber-fiber composite structure is formed.
- the vehicle tire application is amongst the most significant product examples wherein the said composite structure is used.
- the water based RFL adhesives are applied on cord fabric during "dipping" process which is the final step of cord fabric production. The strength of the bonds formed between the rubber and the cord is examined with adhesion tests. Adhesion is a very important parameter in high tenacity cord reinforced rubber products. This is because cord-rubber adhesion is a factor which directly effects the tire life and performance.
- RFL adhesive formulation has been used as an adhesive material in all synthetic fiber reinforced materials for over half a century because of its stable structural features and low cost.
- both resorcinol and formaldehyde are the chemicals which possess high risk for human and environmental health, and therefore their use is limited.
- significant feedbacks have come from international organizations, manufacturers and end users. It is known that the resorcinol causes itching and rash when it contacts the skin, irritates the eye and shows toxic properties in liver and cardiovascular systems.
- Formaldehyde is riskier than resorcinol for human health and safety.
- formaldehyde was classified as group 2A chemical (probably carcinogenic to humans) by a group of scientists in International Agency for Research on Cancer (IARC) of World Health Organization, and later as group 1 (carcinogenic for humans).
- group 2A chemical probably carcinogenic to humans
- group 1 carcinogenic for humans
- formaldehyde was included in the list of chemicals causing leukemia by IARC.
- formaldehyde was claimed to be a gene mutagen. Even low level of formaldehyde (1ppm) can cause eye, nose and throat irritation.
- WO 96/00749 another application known in the state of the art, discloses the application of dipping solutions formulated with three functional-epoxy resins, styrene-butadiene-vinyl pyridine and styrene-butadiene-acrylonitrile-acrylic acid latex to polyethylene terephthalate (PET) cord fabric and its strength of adhesion with rubber.
- PET polyethylene terephthalate
- US 4,472,463 discloses dipping non-adhesive activated PET fibers with two-step dipping process.
- the first dipping step comprises aromatic glycidyl ester epoxy and blocked isocyanate, while the second dipping step comprises two different latexes.
- the first latex is styrene-butadiene-vinyl pyridine copolymer, and the other one is acrylic acid-methyl methacrylate-styrene copolymer. It is stated that the H-adhesion values are higher than that of RFL dipped fibers.
- US 2004/0249053 another application in the state of the art wherein an environmentally friendly dipping material is disclosed, discloses that the maleinized-polybutadiene is rendered water-soluble by reacting with polyethylene glycol.
- the PET cords modified with epoxy are first coated with this resin and then with styrene-butadiene-vinyl pyridine latex.
- the said resin exhibited lower adhesion strength relative to the fabrics treated with RFL.
- JP 2012-224962 discloses a method for producing a resorcinol formaldehyde-free dipping solution comprising epoxy resin, blocked isocyanate, styrene-butadiene-latex and styrene-butadiene-vinyl pyridine latices.
- JP 2002-309220 discloses a first dip composition comprising epoxy resin, blocked isocyanate, vinylpyridine styrene butadiene latex and an acrylic acid resin used as a thickener.
- JP 2011-069020 discloses a resorcinol formaldehyde-free dipping composition comprising an epoxy resin, vinylpyridine styrene butadiene latex, and an acrylic resin which can comprise a polymeric acrylic acid.
- the objective of the present invention is to provide a dipping material, which comprises more environmentally benign chemicals and provides high performance for cord fabrics, instead of the chemicals used in the state of the art.
- Another objective of the present invention is to provide a dipping material production method, which enables the cord fabrics to give the desired effect by being processed for a shorter period of time relative to the method known in the state of the art and provides high performance for cord fabrics.
- a further objective of the present invention is to provide a dipping material providing high performance for cord fabrics which has pale yellow color and thus makes it possible toproduce cords in desired colors.
- dipping material composition providing high performance for cord fabrics, there are functional acrylic resin (polymer) involving carboxylic acid, epoxy resin, blocked polyisocyanate, styrene-butadiene and styrene-butadiene-vinyl pyridine latexes.
- a dipping material composition providing high performance for cord fabrics; which does not have harmful effects on human health in the long term like RFL adhesive solution used in dipping does, and comprises chemicals that are suitable for human health and also environmentally friendly; characterized in that it comprises functional acrylic polymer resin containing carboxylic acid, epoxy resin, blocked polyisocyanate, styrene-butadiene-latex (SBR) and styrene-butadiene-vinyl-pyridine latexes (VP), wherein in its content the acrylic polymer resin is used in a ratio of 0.5-10%, preferably 1.5-5% by weight; the epoxy is 2-10%, preferably 4.5-7% by weight, polyisocyanate is 5-17%, preferably 9-14%; styrene-butadiene latex is 5-17%, preferably 10-13% by weight; styrene-butadiene-vinyl pyridine latex is 50-80%, preferably 65-75% by weight.
- SBR styrene
- the polymers comprising carboxylic acid at least one of the monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid is employed in order to provide functionality to the acrylic resin.
- the amount of carboxylic acid within the acrylic polymer is between 10-100% by mole. In one embodiment of the invention this ratio is preferably kept between 30-70 mol %.
- pH value of this composition comprising water and acrylic polymer is adjusted.
- ammonium is added to the composition to reach a pH value of 7-12, preferably 7-10.
- epoxy is added into the composition.
- the epoxy which is used is either a water soluble epoxy or a water-based dispersion.
- the epoxy at least one of glycidyl-based glycerol, sorbitol epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol propane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerithiole polyglycidyl ether, diglycerol polyglycidyl ether, phenol novalac epoxy, cresol novalac epoxy, cresol novalac and bisphenol A epoxy resins is used.
- Any epoxy which is water soluble or can be prepared as dispersion in water can be used in this invention.
- water-based blocked isocyanate or water-based polyurethane prepolymer comprising blocked polyisocyanate groups is used.
- polyisocyanate at least one of tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic isocyanates 2,4- or 2,6-tolylenediisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4'- or 4-4'-diisocyanatediphenylmethane, 1,3- or 1,4-phenylene diisocyanate is used alone or in the form of functional group attached to the polymers.
- the molecular weight of the waterborne polyurethane prepolymer comprising blocked isocyanate groups is in the range of 1000-10000 g/mol, in one embodiment of
- vinylpyridine-styrene-butadiene vinylpyridine-styrene-butadiene modified with carboxylic acid
- styrene-butadiene vinylpyridine-styrene-butadiene modified with carboxylic acid
- natural latex styrene-butadiene
- chloroprene latex a composition comprising 2 different latexes is used.
- the first latex is styrene-butadiene copolymer and the second is styrene-butadiene-vinyl pyridine terpolymer.
- 1,3-butadiene and 2-methyl-1,3-butadiene can be used as butadiene component, but its use cannot be limited to these.
- Styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropilstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene and hydroxymethylstyrene can be used as styrene component, but its use cannot be limited to these.
- 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine can be used as vinyl pyridine monomer, but the use is not limited to these.
- the solid amount inside the latex is between 35-45% by weight.
- the ratio of the solid of the 1 st latex to that of the 2 nd is in the range of 0.05-1 by weight; however preferably the said ratio should be in the range of 0.13-0.30.
- the dipping material is obtained by adding all the materials mentioned in the previous steps into the water at room temperature and stirring it.
- a method of producing the RFL (resorcinol-formaldehyd) free dipping material composition for cord fabrics as defined above characterized by the steps of:
- compositions were prepared by using acrylic functional polymer, epoxies and polyisocyanates in different ratios.
- the said compositions were made ready for rubber by being dried in different drying and curing temperatures.
- the acrylic resin is used in ratio of 0.5-10%, preferably 1.5-5% by weight; the epoxy is 2-10%, preferably 4.5-7% by weight, polyisocyanate is 5-17%, preferably 9-14% by weight; styrene-butadiene latex is 5-17%, preferably 10-13% by weight; styrene-butadiene-vinyl pyridine latex is 50-80%, preferably 65-75% by weight.
- the invention is a composition which can be used in dipping of cords such as nylon 6.6, nylon 6, polyethylene terephthalate, polyethylene naphthalate, rayon, aramide, and its use is not limited to these.
- cords such as nylon 6.6, nylon 6, polyethylene terephthalate, polyethylene naphthalate, rayon, aramide, and its use is not limited to these.
- the inventive dipping material After the said cords are prepared in certain constructions (ply number and twist), it is dipped with the inventive dipping material and dried at between 100-210°C first. Subsequently, they are cured at between 200-240°C. The dipped cords are made ready to be cured with rubber compound, and it is pressed to the unvulcanized rubber compound.
- the said composite material is generally cured at 170°C under press for about 20 minutes, and the final cord reinforced composite is obtained.
- a method of preparing a cord reinforced composite including a dipping process characterized by the steps of
- the said dipping material composition is prepared using more environmentally friendly chemicals relative to RFL. Furthermore, the said method is advantageous in terms of both cost and short preparation time.
- the final product being pale yellowish does not create any visual pollution and also enables the preparation of cord fabrics in various colors by the addition of colorants.
- the chemicals used in the said invention are acrylic resin, epoxy, polyisocyanate, latex, water and ammonium. Adding and stirring processes were performed via mechanical stirrer under room conditions. The ratios of chemicals used in the preparation of the aqueous composition are given in Table 1 by weight.
- the amount of solids of the mixtures in the present invention was determined as 15%, and pH was adjusted to 9-10 range.
- the indexed peel adhesion strength values are given in Table 1.
- the adhesion of cords dipped with RFL to the rubber was taken as reference, and this value was considered as 100.
- the dipping solution shown as RFL in the invention is the D-5 dipping whose intellectual property rights belong to General Tire Company (USA).
- Two layered 1400 dtex nylon 6.6 yarns were twisted as 396x396, and the twisted cord was dipped into the inventive dipping solutions.
- the cord treated with control (RFL) dipping solution was first dried for 60 seconds at 130 °C, and then cured for 60 seconds at 235 and 230 °C, respectively.
- the dipping solutions in the invention were passed through 3 ovens at different temperatures.
- the temperature of the 1 st oven is kept between 110-210 °C, preferably between 150-200 °C; the temperature of the 2 nd furnace is between 220-245 °C, preferably between 225-240 °C; the temperature of the 3 rd furnace is kept between 210-235 °C, preferably between 220-230 °C.
- acrylic functional polymer (resin) waterborne polymeric materials having 50% solid content and carboxylic acid and polybasic alcohol groups are used.
- Glycerol based glycidyl resin was used as the epoxy. The said resin is 100% water soluble.
- Styrene-butadiene latex is a material with a solid content of 41% and a pH of 10.4.
- Styrene-butadiene-vinyl pyridine is a material with a solid content of 41% and a pH of 10.5.
- Table 1 is a table wherein the peel adhesion values of 3 different inventive mixtures and Resorcinol-Formaldehyde-Latex (RFL) adhesive solution are compared after applying to nylon 6.6 followed by curing.
- Composition Acrylic resin (%) Epoxy (%) Isocyanate (%) SBR latex (%) VP latex (%) Peel adhesion* 1 2,4 6,6 11,1 12,0 68,0 107,9 2 1,8 5,1 13,0 12,0 68,0 103,1 3 4,3 5,5 10,2 12,0 68,0 101,4 Control (RFL) 100,0 *indexed
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Description
- The present invention relates to an environmentally friendly dipping material composition, which forms an interphase between the synthetic fiber that is used in the production of cord fabric and rubber and thus bonds the said two structures to each other.
- Cord fabric is used as tire reinforcement material. Since the chemical structures of synthetic fibers used in cord fabric production and rubber are considerably different from each other, the said materials are incompatible with each other in terms of their chemical and physical structures. Synthetic fibers have high strength and low elongation whereas rubbers are polymeric materials which have high elongation and low strength. The polar groups (amide, hydroxyl and carbonyl groups) present in the structure of the synthetic fibers are incompatible with the non-polar structures of the rubber. This incompatibility present in the state of the art is eliminated with water-based Resorcinol-Formaldehyde-Latex (RFL) adhesive solutions which form a phase between the cord and the rubber and enable the rubber and the fiber to be attached to each other.
- Main function of RFL is to serve as an adhesive bonding two incompatible structures by forming a phase between fiber and rubber. RF functional group in RFL is attached to the polar groups of fiber while Latex (L) group is attached to the fiber by vulcanization, and thus the rubber-fiber composite structure is formed. The vehicle tire application is amongst the most significant product examples wherein the said composite structure is used. The water based RFL adhesives are applied on cord fabric during "dipping" process which is the final step of cord fabric production. The strength of the bonds formed between the rubber and the cord is examined with adhesion tests. Adhesion is a very important parameter in high tenacity cord reinforced rubber products. This is because cord-rubber adhesion is a factor which directly effects the tire life and performance.
- RFL adhesive formulation has been used as an adhesive material in all synthetic fiber reinforced materials for over half a century because of its stable structural features and low cost. However, both resorcinol and formaldehyde are the chemicals which possess high risk for human and environmental health, and therefore their use is limited. Regarding this subject, significant feedbacks have come from international organizations, manufacturers and end users. It is known that the resorcinol causes itching and rash when it contacts the skin, irritates the eye and shows toxic properties in liver and cardiovascular systems.
- Formaldehyde is riskier than resorcinol for human health and safety. In 2004, formaldehyde was classified as group 2A chemical (probably carcinogenic to humans) by a group of scientists in International Agency for Research on Cancer (IARC) of World Health Organization, and later as group 1 (carcinogenic for humans). In 2009, formaldehyde was included in the list of chemicals causing leukemia by IARC. In line with this, formaldehyde was claimed to be a gene mutagen. Even low level of formaldehyde (1ppm) can cause eye, nose and throat irritation.
- Although formaldehyde-based resins are advantageous in terms of cost, both producers and consumers search for alternatives because of the reasons stated above. Therefore, especially in recent years, researchers have been working on the development of resorcinol and formaldehyde-free cord fabric dip solutions. The preparation of formaldehyde-free dip solutions have been reported in various studies.
-
US 2012/0041113 , an application known in the state of the art, discloses preparing a composition comprising an epoxy, a blocked isocyanate, an epoxy curing agent and vinyl pyridine latex. -
WO 96/00749 -
US 5,118,545 , another application known in the state of the art, discloses the synthesis of an aramide comprising multiple double bonds. It is stated that the synthesized resin is applied on the aramide-based cord fabric and that the double bonds in the aramide resin are vulcanized with the double bonds in rubber while the amide groups provide physical adhesion to the aramide fiber. -
US 4,472,463 discloses dipping non-adhesive activated PET fibers with two-step dipping process. The first dipping step comprises aromatic glycidyl ester epoxy and blocked isocyanate, while the second dipping step comprises two different latexes. The first latex is styrene-butadiene-vinyl pyridine copolymer, and the other one is acrylic acid-methyl methacrylate-styrene copolymer. It is stated that the H-adhesion values are higher than that of RFL dipped fibers. -
US 2004/0249053 , another application in the state of the art wherein an environmentally friendly dipping material is disclosed, discloses that the maleinized-polybutadiene is rendered water-soluble by reacting with polyethylene glycol. The PET cords modified with epoxy are first coated with this resin and then with styrene-butadiene-vinyl pyridine latex. The said resin exhibited lower adhesion strength relative to the fabrics treated with RFL. -
JP 2012-224962 JP 2002-309220 JP 2011-069020 - The objective of the present invention is to provide a dipping material, which comprises more environmentally benign chemicals and provides high performance for cord fabrics, instead of the chemicals used in the state of the art.
- Another objective of the present invention is to provide a dipping material production method, which enables the cord fabrics to give the desired effect by being processed for a shorter period of time relative to the method known in the state of the art and provides high performance for cord fabrics.
- A further objective of the present invention is to provide a dipping material providing high performance for cord fabrics which has pale yellow color and thus makes it possible toproduce cords in desired colors.
- In an inventive dipping material composition providing high performance for cord fabrics, there are functional acrylic resin (polymer) involving carboxylic acid, epoxy resin, blocked polyisocyanate, styrene-butadiene and styrene-butadiene-vinyl pyridine latexes. Thus, according to the present invention, there is provided a dipping material composition providing high performance for cord fabrics; which does not have harmful effects on human health in the long term like RFL adhesive solution used in dipping does, and comprises chemicals that are suitable for human health and also environmentally friendly; characterized in that it comprises functional acrylic polymer resin containing carboxylic acid, epoxy resin, blocked polyisocyanate, styrene-butadiene-latex (SBR) and styrene-butadiene-vinyl-pyridine latexes (VP), wherein in its content the acrylic polymer resin is used in a ratio of 0.5-10%, preferably 1.5-5% by weight; the epoxy is 2-10%, preferably 4.5-7% by weight, polyisocyanate is 5-17%, preferably 9-14%; styrene-butadiene latex is 5-17%, preferably 10-13% by weight; styrene-butadiene-vinyl pyridine latex is 50-80%, preferably 65-75% by weight. In the polymers comprising carboxylic acid, at least one of the monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid is employed in order to provide functionality to the acrylic resin. In the preferred embodiment of the invention, the amount of carboxylic acid within the acrylic polymer is between 10-100% by mole. In one embodiment of the invention this ratio is preferably kept between 30-70 mol %. Then, pH value of this composition comprising water and acrylic polymer is adjusted. In the preferred embodiment of the invention, ammonium is added to the composition to reach a pH value of 7-12, preferably 7-10. After pH is adjusted to the desired level, epoxy is added into the composition. In the preferred embodiment of the invention, the epoxy which is used is either a water soluble epoxy or a water-based dispersion. As the epoxy, at least one of glycidyl-based glycerol, sorbitol epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol propane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerithiole polyglycidyl ether, diglycerol polyglycidyl ether, phenol novalac epoxy, cresol novalac epoxy, cresol novalac and bisphenol A epoxy resins is used. However their use is not limited to these. Any epoxy which is water soluble or can be prepared as dispersion in water can be used in this invention.
- In the preferred embodiment of the invention, water-based blocked isocyanate or water-based polyurethane prepolymer comprising blocked polyisocyanate groups is used. As polyisocyanate, at least one of tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic isocyanates 2,4- or 2,6-tolylenediisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4'- or 4-4'-diisocyanatediphenylmethane, 1,3- or 1,4-phenylene diisocyanate is used alone or in the form of functional group attached to the polymers. At least one of phenol, thiophenol, chlorophenol, cresol resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, tert-butyl alcohol, diphenylamine, dimethyl aniline, phthalic imide, δ-valerolactam, ε-caprolactam, malonic acid dialkylester, acetylacetone, acetoacetic acid alkylester, acetoxime, methylethylketoxime, cyclohexanone oxime, 3-hydroxypyridine and acidic sodium sulfite can be used as free isocyanate blocking agent, but their use is not limited to these. In the preferred embodiment of the invention, the molecular weight of the waterborne polyurethane prepolymer comprising blocked isocyanate groups is in the range of 1000-10000 g/mol, in one embodiment of the invention this value is between 1500-3000g/mol.
- In the invention, vinylpyridine-styrene-butadiene, vinylpyridine-styrene-butadiene modified with carboxylic acid, styrene-butadiene, styrene-butadiene modified with carboxylic acid, natural latex, chloroprene latex and the like can be used. In the invention, a composition comprising 2 different latexes is used. The first latex is styrene-butadiene copolymer and the second is styrene-butadiene-vinyl pyridine terpolymer. 1,3-butadiene and 2-methyl-1,3-butadiene can be used as butadiene component, but its use cannot be limited to these. Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropilstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene and hydroxymethylstyrene can be used as styrene component, but its use cannot be limited to these. 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine can be used as vinyl pyridine monomer, but the use is not limited to these. In the preferred embodiment of the invention, the solid amount inside the latex is between 35-45% by weight. The ratio of the solid of the 1st latex to that of the 2nd is in the range of 0.05-1 by weight; however preferably the said ratio should be in the range of 0.13-0.30.
- The dipping material is obtained by adding all the materials mentioned in the previous steps into the water at room temperature and stirring it. Thus, according to an embodiment of the invention, there is provided a method of producing the RFL (resorcinol-formaldehyd) free dipping material composition for cord fabrics as defined above, characterized by the steps of:
- adding acrylic polymer resin containing carboxylic acid into water,
- adjusting the pH value to 7-12 by adding ammonium,
- adding epoxy resin, blocked polyisocyanate, styrene-butadiene-latex (SBR) and styrene-butadiene-vinyl-pyridine latexes (VP) at room temperature, and
- stirring.
- The compositions were prepared by using acrylic functional polymer, epoxies and polyisocyanates in different ratios. The said compositions were made ready for rubber by being dried in different drying and curing temperatures.
- In the invention, the acrylic resin is used in ratio of 0.5-10%, preferably 1.5-5% by weight; the epoxy is 2-10%, preferably 4.5-7% by weight, polyisocyanate is 5-17%, preferably 9-14% by weight; styrene-butadiene latex is 5-17%, preferably 10-13% by weight; styrene-butadiene-vinyl pyridine latex is 50-80%, preferably 65-75% by weight.
- The invention is a composition which can be used in dipping of cords such as nylon 6.6, nylon 6, polyethylene terephthalate, polyethylene naphthalate, rayon, aramide, and its use is not limited to these. After the said cords are prepared in certain constructions (ply number and twist), it is dipped with the inventive dipping material and dried at between 100-210°C first. Subsequently, they are cured at between 200-240°C. The dipped cords are made ready to be cured with rubber compound, and it is pressed to the unvulcanized rubber compound. The said composite material is generally cured at 170°C under press for about 20 minutes, and the final cord reinforced composite is obtained.
- Thus, according to another embodiment of the invention, there is provided a method of preparing a cord reinforced composite including a dipping process characterized by the steps of
- preparing cords in determined construction (ply number and twist),
- treating the prepared cords with the dipping material composition as defined above,
- drying the dipped cords at 100-210 °C,
- curing the dried cords at 200-240 °C,
- making the cords ready to be cured with the rubber compound,
- pressing the unvulcanized rubber compound,
- curing the resulting composite material at a temperature of 170 °C under press for about 20 minutes,
- obtaining the final composite material reinforced with cord.
- The said dipping material composition is prepared using more environmentally friendly chemicals relative to RFL. Furthermore, the said method is advantageous in terms of both cost and short preparation time. The final product being pale yellowish does not create any visual pollution and also enables the preparation of cord fabrics in various colors by the addition of colorants.
- The chemicals used in the said invention are acrylic resin, epoxy, polyisocyanate, latex, water and ammonium. Adding and stirring processes were performed via mechanical stirrer under room conditions. The ratios of chemicals used in the preparation of the aqueous composition are given in Table 1 by weight.
- The amount of solids of the mixtures in the present invention was determined as 15%, and pH was adjusted to 9-10 range. The indexed peel adhesion strength values are given in Table 1. The adhesion of cords dipped with RFL to the rubber was taken as reference, and this value was considered as 100. The dipping solution shown as RFL in the invention is the D-5 dipping whose intellectual property rights belong to General Tire Company (USA). Two layered 1400 dtex nylon 6.6 yarns were twisted as 396x396, and the twisted cord was dipped into the inventive dipping solutions. The cord treated with control (RFL) dipping solution was first dried for 60 seconds at 130 °C, and then cured for 60 seconds at 235 and 230 °C, respectively. The dipping solutions in the invention were passed through 3 ovens at different temperatures. The temperature of the 1st oven is kept between 110-210 °C, preferably between 150-200 °C; the temperature of the 2nd furnace is between 220-245 °C, preferably between 225-240 °C; the temperature of the 3rd furnace is kept between 210-235 °C, preferably between 220-230 °C.
- Five cords were placed parallel to each other on the rubber mixture for the adhesion test. The said mixture was cured at 170 °C under press, and then tested by pulling in Instron device. Here, the detachment value of the cord from the cured rubber was measured as kg.
- As the acrylic functional polymer (resin) waterborne polymeric materials having 50% solid content and carboxylic acid and polybasic alcohol groups are used. Glycerol based glycidyl resin was used as the epoxy. The said resin is 100% water soluble.
- Water based, caprolactam blocked 1,4-phenylene diisocyanate with 60% solid content was used as the blocked polyisocyanate.
- Styrene-butadiene latex is a material with a solid content of 41% and a pH of 10.4.
- Styrene-butadiene-vinyl pyridine is a material with a solid content of 41% and a pH of 10.5.
Table 1 is a table wherein the peel adhesion values of 3 different inventive mixtures and Resorcinol-Formaldehyde-Latex (RFL) adhesive solution are compared after applying to nylon 6.6 followed by curing. Composition Acrylic resin (%) Epoxy (%) Isocyanate (%) SBR latex (%) VP latex (%) Peel adhesion* 1 2,4 6,6 11,1 12,0 68,0 107,9 2 1,8 5,1 13,0 12,0 68,0 103,1 3 4,3 5,5 10,2 12,0 68,0 101,4 Control (RFL) 100,0 *indexed
Claims (16)
- A dipping material composition providing high performance for cord fabrics; which does not have harmful effects on human health in the long term like RFL adhesive solution used in dipping does, and comprises chemicals that are suitable for human health and also environmentally friendly; characterized in that it comprises functional acrylic polymer resin containing carboxylic acid, epoxy resin, blocked polyisocyanate, styrene-butadiene-latex (SBR) and styrene-butadiene-vinyl-pyridine latexes (VP), wherein in its content the acrylic polymer resin is used in a ratio of 0.5-10%, preferably 1.5-5% by weight; the epoxy is 2-10%, preferably 4.5-7% by weight, polyisocyanate is 5-17%, preferably 9-14%; styrene-butadiene latex is 5-17%, preferably 10-13% by weight; styrene-butadiene-vinyl pyridine latex is 50-80%, preferably 65-75% by weight.
- The dipping material composition providing high performance for cord fabrics according to claim 1, characterized by an acrylic polymer resin which comprises carboxylic acid formed with at least one of the monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid in order to provide its functionality.
- The dipping material composition providing high performance for cord fabrics according to claim 1 or 2, characterized by an acrylic polymer resin wherein the carboxylic acid content therein is 10-100% by mole and the said value is preferably kept between 30-70%.
- The dipping material composition providing high performance for cord fabrics according to any one of the preceding claims, characterized by an epoxy resin which is water soluble or a water based dispersion and which is at least one of glycidyl based glycerol, sorbitol epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol propane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, phenol novalac epoxy, cresol novalac epoxy, cresol novalac and bisphenol A epoxy resins.
- The dipping material composition providing high performance for cord fabrics according to any one of the preceding claims, characterized by a blocked polyisocyanate used in blocked form which is from the group of either water based blocked polyisocyanates or water based polyurethane prepolymers comprising blocked polyisocyanates and is at least one of tetramethylene diisocyanate, hexamethylene disocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic isocyanates 2,4- or 2,6-tolylene diisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4'- or 4-4'-diisocyanatediphenylmethane, 1,3- or 1,4-phenylene diisocyanate is used alone and in the form of a functional group attached to the polymer.
- The dipping material composition providing high performance for cord fabrics according to any one of the preceding claims, characterized by a blocked polyisocyanate which is obtained by blocking free isocyanates with at least one of the blocking agents selected from the group comprising phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, tert-butyl alcohol, diphenylamine, dimethylaniline, phthalic imide, δ-valerolactam, ε-caprolactam, malonic acid dialkylester, acetylacetone, acetoacetic acid alkylester, acetoxime, methylethylcetoxime, cyclohexanonoxime, 3-hydroxypyridine and acidic sodium sulfite.
- The dipping material composition providing high performance for cord fabrics according to any one of the preceding claims, characterized by a water based polyurethane prepolymer comprising blocked isocyanate groups, the molecular weight of which is in the range of 1000-10000 g/mol and preferably 1500-3000 g/mol.
- The dipping material composition providing high performance for cord fabrics according to any one of the preceding claims, characterized in that at least one latex selected from the group comprising vinylpyridine-styrene-butadiene, vinylpyridine-styrene-butadiene modified with carboxylic acid, styrene-butadiene, and styrene-butadiene modified with carboxylic acid, is used as the SBR or VPlatex.
- The dipping material composition providing high performance for cord fabrics according to claim 8, characterized by a latex wherein the butadiene component in the structure is 1,3-butadiene and 2-methyl-1,3-butadiene.
- The dipping material composition providing high performance for cord fabrics according to claim 8, characterized in that a latex is used wherein the styrene component in its structure is styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene and hydroxymethylstyrene.
- The dipping material composition providing high performance for cord fabrics according to claim 8, characterized in that a latex is used wherein 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine is used as the vinyl pyridine monomer within the structure.
- The dipping material composition providing high performance for cord fabrics according to claims 8 to 11, characterized in that latices with a solid content of between 35-45% are used.
- The dipping material composition providing high performance for cord fabrics according to claim 8, characterized in that the ratio of the solid content of styrene-butadiene latex to that of styrene-butadiene-vinylpyridine latex is in the range of 0.05-1 by weight, preferably in the range of 0.13-0.30.
- A method of producing the RFL (resorcinol-formaldehyd) free dipping material composition for cord fabrics as defined in any one of claims 1 to 13, characterized by the steps of:- adding acrylic polymer resin containing carboxylic acid into water,- adjusting the pH value to 7-12 by adding ammonium,- adding epoxy resin, blocked polyisocyanate, styrene-butadiene-latex (SBR) and styrene-butadiene-vinyl-pyridine latexes (VP) at room temperature, and- stirring.
- A method of preparing a cord reinforced composite including a dipping process characterized by the steps of- preparing cords in determined construction (ply number and twist),- treating the prepared cords with the dipping material composition according to any one of the preceding claims,- drying the dipped cords at 100-210 °C,- curing the dried cords at 200-240 °C,- making the cords ready to be cured with the rubber compound,- pressing the unvulcanized rubber compound,- curing the resulting composite material at a temperature of 170 °C under press for about 20 minutes,- obtaining the final composite material reinforced with cord.
- The method of claim 15, wherein the cord is selected from nylon 6.6, nylon 6, polyethylene terephthalate, polyethylene naphthalate, rayon, or aramide.
Priority Applications (2)
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PL14736054T PL2989243T3 (en) | 2013-04-26 | 2014-04-22 | A rfl-free dipping composition providing high performance for cord fabrics |
SI201430328T SI2989243T1 (en) | 2013-04-26 | 2014-04-22 | A rfl-free dipping composition providing high performance for cord fabrics |
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TR201305016 | 2013-04-26 | ||
PCT/TR2014/000123 WO2014175844A2 (en) | 2013-04-26 | 2014-04-22 | A dipping material providing high performance for cord fabrics |
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EP2989243B1 true EP2989243B1 (en) | 2017-06-07 |
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US (1) | US10145034B2 (en) |
EP (1) | EP2989243B1 (en) |
KR (1) | KR101719190B1 (en) |
CN (1) | CN105051284B (en) |
BR (1) | BR112015017863B1 (en) |
ES (1) | ES2629102T3 (en) |
LU (1) | LU92623B1 (en) |
PL (1) | PL2989243T3 (en) |
SI (1) | SI2989243T1 (en) |
WO (1) | WO2014175844A2 (en) |
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CN109252377A (en) * | 2017-07-13 | 2019-01-22 | 北京化工大学 | A kind of fibre framework materials dipping solution, preparation method and dipping method |
CN107236494B (en) * | 2017-07-17 | 2019-01-29 | 山东奥固特化工科技有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
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CN107804979B (en) * | 2017-11-08 | 2020-05-26 | 四川省玻纤集团有限公司 | Chopped basalt fiber impregnating compound for reinforced rubber and preparation method thereof |
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CN109371683A (en) * | 2018-08-14 | 2019-02-22 | 江志平 | A kind of rubber product fiber skeleton impregnation material and its preparation and application |
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CN109097993A (en) * | 2018-09-10 | 2018-12-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
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EP3702523A1 (en) | 2019-03-01 | 2020-09-02 | Continental Reifen Deutschland GmbH | Aqueous dipping composition |
EP3702524A1 (en) | 2019-03-01 | 2020-09-02 | Continental Reifen Deutschland GmbH | Aqueous dipping composition |
CN112176729A (en) | 2019-07-03 | 2021-01-05 | 北京化工大学 | Nano-reinforced environment-friendly impregnation system for fiber surface treatment, preparation method and impregnation method |
CN110284326B (en) * | 2019-07-06 | 2021-12-31 | 蔚林新材料科技股份有限公司 | Green environment-friendly glue dipping solution and production method thereof |
CN110951416A (en) * | 2019-11-21 | 2020-04-03 | 淄博奥固特科技有限公司 | Triisocyanate adhesive, preparation method and application thereof |
WO2021206471A1 (en) * | 2020-04-09 | 2021-10-14 | 코오롱인더스트리 주식회사 | Adhesive composition and rubber reinforcing material |
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CN115748256A (en) * | 2021-09-02 | 2023-03-07 | 北京化工大学 | Environment-friendly impregnation system for fiber surface treatment, preparation method thereof and impregnation treatment method |
WO2023155989A1 (en) | 2022-02-17 | 2023-08-24 | Continental Reifen Deutschland Gmbh | Composite material for elastomeric products, in particular vehicle tyres, and method for manufacturing same |
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WO2014175844A2 (en) | 2014-10-30 |
BR112015017863B1 (en) | 2022-06-07 |
EP2989243A2 (en) | 2016-03-02 |
BR112015017863A8 (en) | 2018-07-31 |
WO2014175844A3 (en) | 2015-01-29 |
CN105051284A (en) | 2015-11-11 |
PL2989243T3 (en) | 2017-10-31 |
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